Chapter 16

Solubility and Complex Ion Equilibria

Basic Questions
Basic question 1
Calculate the Ksp of Al(OH)3 given that its solubility is 1.0 x 10 –11M.
Given: solubility = 1.0 x 10-11 RTF: Ksp

Al(OH)3(s) ⇆ Al+3(aq) + 3OH-(aq)

[initially] --- - -
[change] -s +s +3s
[eqbm] -- s 3s

Ksp = [Al3+][OH-]3 = (s)(3s)3 = 27s4 = 27(1.0 x 10-11)4 Ksp = 2.7 x 10-43

Basic question 2
The Ksp of Mg(OH)2 is 4.0 x 10-12. Calculate the solubility of Mg(OH)2 in water.
Given: Ksp = 4.0 x 10-12 RTF: solubility

Mg(OH)2(s) ⇆ Mg2+(aq) + 2OH-(aq)

[initially] --- - -
[change] -s +s +2s
[eqbm] -- s 2s

Ksp = [Mg2+][OH-]2 = (s)(2s)2 = 4s3 = 4.0 x 10-12 s = 1.0 x 10-4 M

Basic question 3
The Ksp of AgCl is 1.0 x 10-10. Calculate the maximum mass of AgCl that will dissolve in
500cm3 solution.
Given: Ksp = 1.0 x 10-10, V = 500ml RTF: mass of AgCl that dissolves

AgCl(s) ⇆ Ag+(aq) + Cl-(aq)

[initially] --- - -
[change] -s +s +s
[eqbm] -- s s
+ - 2 -10
Ksp = [Ag ][Cl ] = (s)(s) = s = 1.0 x 10
s = 1.0 x 10-5 M
 1.0 x 10-5 moles dissolve in 1000ml solution
? moles dissolve in 500mL solution
-6
? = 5.0 x 10 mole n=  m = nM = (5.0 x 10-6)(143.5) = 7.18 x 10-4 g
Basic question 4
The Ksp of PbSO4 is 1.0 x 10-8. Calculate the solubility of PbSO4 in 0.010M Pb(NO3)2(aq)
solution.
Given: Ksp = 1.0 x 10-8, [Pb(NO3)2] = 0.010M RTF: solubility

PbSO4(s) ⇆ Pb+2(aq) + SO4-2(aq)

[initially] --- 0.010 -
[change] -s +s +s
[eqbm] -- 0.010 + s s

Ksp = [Pb+2][SO4-2] = (s)(s+0.010) = 1.0 x 10-8 assume s << 0.010M

s = 1.0 x 10-6 M (valid assumption)

Basic question 5
A solution in which the [Ca2+] is 0.20 M was prepared. Calculate the minimum pH needed to
precipitate the Ca2+ ions as Ca(OH)2 from the solution.
Ksp Ca(OH)2 = 1.3 x 10-6.
Given: Ksp = 1.3 x 10-6, [Ca2+] = 0.20M RTF: pH to initiate precipitation

Ksp = [Ca2+][OH-]2 = (0.20)[OH-]2 = 1.3 x 10-6

 [OH-] = 2.55 x 10-3M pOH = 2.59 pH = 11.40

Basic question 6
A sample containing 20ml of 1.0 x 10-4 M AgNO3 solution were mixed with 30ml of 1.0 x 10-3
M NaBr solution. Will a precipitate form? Ksp of AgBr = 5.0 x 10-13.
Given: [AgNO3] = 1.0 × 10-4 M, VAgNO3 = 20ml, [NaBr] = 1.0 × 10-3 M, VNaBr = 30ml
Ksp = 5.0 × 10-13
RTF: Will a ppt form?
Step 1: Calculate new concentrations

.
[Ag+]new = = 4.0 × 10-5M

.
[Br-]new = = 6.0 × 10-4M

Step 2: Calculate mass action expression, Q

-5 -4 -8
Q = [Ag+][Br-] = (4.0 × 10 )( 6.0 × 10 ) = 2.4 × 10

Step 3: Compare Q to Ksp Q > Ksp, a precipitate will form

Basic question 7
Answer the following question relating to the solubility of the bromides of silver and lead.
a) At 10C, 1.0 x 10-6g of AgBr(s) will dissolve in 100ml of water.

i. Write the dissociation of AgBr(s) in water. AgBr(s)  Ag+(aq) + Br-(aq)

ii. Calculate the solubility, in mol L-1, of AgBr(s) in water at 10oC.
Given: mAgBr = 1.0 x 10-6g, V = 100ml
RTF = solubility
Solubility is the molar concentration of a saturated solution.
. .
n= = 5.3 × 10-9 mole solubility = = 5.3 × 10-8 M
.
iii. Calculate the value of the solubility product constant, Ksp for AgBr(s) at 10oC.
Given: s = 5.3 × 10-8 M
RTF: Ksp
AgBr(s) ⇆ Ag+(aq) + Br-(aq)
[initially] --- - -
[change] -s +s +s
[eqbm] -- s s
+ - 2 -8 2 -15
Ksp = [Ag ][Br ] = (s)(s) = s = (5.3 × 10 ) = 2.8 × 10

b) At 25oC, the value of the Ksp for PbBr2 is 4.0 x 10-6 and the value of the Ksp of AgBr is 4.0
x 10-15
i. If 60.0ml of 0.100M NaBr(aq) is added to 60.0ml of 0.400M Pb(NO3)2(aq), will a
precipitate form? Assume volumes are additive. Show calculations to support your
answer.
Given: [Pb(NO3)2] = 0.400 M, VPb(NO3 )2 = 60.0ml, [NaBr] = 0.100M, VNaBr = 60.0ml,
Ksp PbBr2 = 4.0 × 10-6 , Ksp AgBr = 4.0 × 10-15 RTF: Will a ppt form?

. .
[Pb2+]new = = 0.200M [Br-]new = = 0.0500M

2
Q = [Pb+2][Br-]2 = (0.200)(0.0500) = 5.0 × 10-4 Q > Ksp, a precipitate will form

ii.Calculate the equilibrium value of [Pb2+] in 1.00L of saturated PbBr2 solution to

which 0.200 mole of NaBr(s) has been added. Assume that no volume change
occurs.
Given: nNaBr = 0.200mole, V = 1.00L, Ksp = 4.0 x 10-6 RTF: [Pb2+]

. .
[Br-] = = 0.200M Ksp = [Pb2+][Br-]2 [Pb2+] = = 1.0 × 10-4M
. .

iii.
If 0.100M NaBr(aq) is added slowly to a beaker containing both 0.120M
AgNO3(aq) and 0.150M Pb(NO3)2(aq) at 25oC, which will precipitate first AgBr(s)
or PbBr2(s)? Show calculations to support your answer.
Given: For AgBr Ksp = 4.0 x 10-15 For PbBr2 Ksp = 4.0 x 10-6 RTF: which ppts first?
 Molar solubility of AgBr at 25C
Ksp = s 2 = 4.0  10-15

s= 4.0 x10-15 = 6.3  10-8 M

Molar solubility of PbBr2 at 25C

Ksp 4.0 x10-6

Ksp = 4s3 and s = 3
= =1.0  10-2 M
4 4

Therefore, AgBr will precipitate first.

OR For AgBr Ksp = 4.0 × 10-15 = [Ag+][Br-]

.
[Br-] = = 3.33 × 10-14
.

For Pb(Br)2 Ksp = 4.0 × 10-6 = [Pb+2][Br-]2

.
[Br-] = = 5.16 × 10-3M
.

Therefore, AgBr will precipitate first since it requires much less bromide ions
to precipitate.

Basic Question 8
16.2 Given quantities of one ion, calculate min quantity of another ion needed to T, G
precipitate it
A student added 0.50 mole of NaCl and 0.25 mole of CaCl2 to 5.0 L of water making an aqueous
solution. What is the minimum number of moles of AgNO3 required to precipitate all the Cl-
ions into AgCl?
Given: nNaCl = 0.50 mole, = 0.25 mole
RTF: n of AgNO3 to ppt the chloride ions

Total n of Cl- = 0.50 + 2(0.25) = 1.0 mole

Since Ksp of AgCl = 1 × 10-10, assume complete precipitation
Ag+(aq) + Cl-(aq)  AgCl(s)  = = 1.0 mole

Basic Question 9
16.2 Given [ ] and V of two solutions list the ions remaining after a precipitate forms T, G
in order
A student added 0.50 L of 1.0M NaCl to 0.50 L of 1.0 M of Pb(NO3)2. List the ions remaining
after precipitation in order of increasing concentration.
Given: VNaCl = 0.50 L, [NaCl] = 1.0M, = 0.50 L, [Pb(NO3)2] = 1.0 M
RTF: [all ions]
 .
Na+ and NO3- do not react, [Na+] = = 0.50 M
.
.
[NO3-] =2 × = 1.0 M
.
= 0.50 mole
= 0.50 mole
Pb+2(aq) + 2Cl-(aq)  PbCl2(s)  Pb2+ in excess

left = 0.50 – 0.25 = 0.25 mole [Pb2+] = 0.25 M

[Pb2+] < [Na+] < [NO3-]

Basic Question 10

16.2 Find the solubility product of an insoluble hydroxide given [OH-] of a saturated
solution

In a saturated solution of Zn(OH)2 at 25◦C, the value of [OH-] is 2.0 x 10-6M. What is the value
of the solubility product constant, Ksp, for Zn(OH)2 at 25◦C?

Zn(OH)2(s) ⇆ Zn+2(aq) + 2OH-(aq)

[initially] --- - -
[change] -s +s +2s
[eqbm] -- s 2s

2s = 2.0 × 10-6 s = 1.0 × 10-6

Ksp = [Zn ][OH ] = (s)(2s) = 4s = 4(1.0 × 10-6)3 = 4.0 × 10-18
+2 - 2 2 3

[-A-] 4.0 × 10–18

[-B-] 8.0 × 10–18
[-C-] 1.6 × 10–17
[-D-] 4.0 × 10–12
[-E-] 2.0 × 10–6
SAMPLE QUESTIONS

Section 16.1

1. Know how to write the dissociation equation for a given sparingly soluble compound
Write the dissocation equation of lead(II) iodide.
PbI2(s) ⇌ Pb2+(aq) + 2I-(aq)

2. Know how to write Ksp expression for a given sparingly soluble compound
Write the Ksp expression for PbI2. Ksp = [Pb2+][I-]2

3. Know that molar solubility is the concentration of a saturated solution.

Define molar solubility?
It is the molar concentration of a saturated solution.

4. Using Q to see if solution is saturated or not

A solution is prepared in which the [Cl-] and [Ag+] are respectively 1.0  10-6 M and
1.0 × 10-5M. Is this solution saturated in AgCl? Ksp of AgCl = 1.0  10-10.
To answer, we must calculate the mass action expression, Q.
If Q < K, reaction is proceeding to the right towards forming products, not
saturated.
If Q = K, reaction is at equilibrium and is saturated.
If Q > K, reaction is proceeding to the left and is saturated.

Q = [Ag+][Cl-] = (1.0 × 10-6)( 1.0 × 10-5) = 1.0 × 10-11 < Q, solution is NOT saturated.

5. Find an expression for Ksp in terms of a given solubility

If the solubility of AgCl is x, write an expression that is equal to Ksp in terms of x.

AgCl(s) ⇌ Ag+(aq) + Cl-(aq)

[initial] ----- 0 0
[change] -x +x +x
[equilibrium] ----- x x

Ksp = [Ag+][Cl-] = x2
x=
Section 16.2

6. Know that solubility of weak bases decreases as the pH of the solution increases
Silver hydroxide is least soluble in a solution of
pH = 2, pH = 4, pH = 7, pH = 10 or pH = 12
As pH increases, [OH-] increases and solubility of bases in such solutions decreases.
Silver hydroxide is least soluble in a solution of pH = 12

7. Know that solubility of a compound decreases as the [common ion] increases in the
solution
Lead(II) iodide will be least soluble in a 0.20M solution of which of the following?
NaI, PbNO3, CaI2 or Pb(CH3COO)2.
CaI2, [I-] = 2[CaI2] = 0.40M, highest concentration of common ion.